The Bloch Equations :

We define a quantity called the bulk magnetic moment. This is the macroscopic
version of the microscopic magnetic moments of the nuclei in the sample and is the
vector sum of all magnetic moments in the bulk of the material of interest:

At the instant they are put into the field there will be a completely random distribution
of magnetic moments in all directions. The bulk magnetic moment (or net
magnetisation) is therefore zero. After some time however this changes and a net
magnetic moment, M, appears, aligned with the external magnetic field,
, and the
spin system is said to be at equilibrium.

At equilibrium this magnetisation vector is aligned parallel to the z-axis as is the

external magnetic field, . Imagine that we now move this vector away from its
equilibrium position in some as yet unspecified way and that the vector, now labelled
since it is not in the equilibrium position, is not co-linear with the x, y or z axes. We
can break down into its component vectors along the axes:

Vector

, being at an angle with respect to the z-axis and therefore

the applied field , will precess about the z-axis, just as the individual magnetic
moments will. Assuming that there will no relaxation of back to the equilibrium
position along the z-axis and that it will precess indefinitely we can write:

remembering that the field is parallel to the z-axis and has no components in the xy plane.
of course unit basis vectors. This result tells us that the
magnetisation changes in the x-y plane but not along the z-axis. In other words the
magnetisation vector, , precesses about the z-axis as shown in the figure. Since
the projection of
onto the z-axis will (obviously) not precess about the z-axis we
can write:

This should also be evident from the fact that

is at right angles to the plane
defined by
and
and will therefore have no component on the z-axis.
is
called the longitudinal magnetisation.
Now magnetisation in the transverse (the x-y) plane :

This case there is a magnetisation

taking place.

in an external field

and there is no relaxation

Before we take into account relaxation let's look at the situation when a linearly
oscillating electromagnetic field,
moving back and forth along the x-axis is
applied at right angles to the external field, .Conceptually, the
field may then be
broken up into two counter-rotating vectors the sum of which always is
.We will
call these new vectors
and
for the moment and assign a rotational
frequency of + and
to them. The x and y components of these two counterrotating vectors are contained in:

Only one of these two fields will concern us since the other is rotating with a
negative frequency relatively speaking and does not affect any spins. We choose
one and ignore the other.
So, now we have two fields to consider,
and .
is, of course, static and
aligned along the z-axis (or more accurately, the z-axis is aligned with ) and is
at 90 degrees to the z-axis and rotating about the z-axis at
radians per second.
We can call the sum of these two vectors

Obviously, since
is rotating about the z-axis,
is rotating about the z-axis as
well. The size of
is much exaggerated in the figure. Generally,
so that is
only slightly off of the z-axis. Our new simple Bloch equations (still without relaxation
taken into account) are:

remembering that
therefore

is along the z-axis and

is in the transverse plane and
are zero. The rates of change of each component of are:

Now lets involve the Rotating Frame of Reference :

(
) refers to the rotation of the x,y and z-axes at vector frequency We are
completely free to choose what that frequency is so we choose the frequency of the
rotating

field,

Now, we have

Lets put

into the equation now :

And define a fictitious field

So, we have

and

and

and

is the Larmor frequency of a spin in

the static field,

and is itself constant.
is the magnetisation due to the sum of
the magnetic moments in the collection of (many, many) spins in the sample.
is
the rotating magnetic component of the applied electromagnetic field.
is the
frequency of the rotating frame of reference which is also the frequency of the
field.
What will happen if we vary
from zero up to
? The term corresponds to our
'fictitious field',
, and will at first be equal to when
is zero. As
increases
the value of
decreases and the vector sum, , of
and
begins to tilt slowly
towards the x-y plane. As
approaches
the rate of tilt increases until at
is entirely in the x-y plane. In other words,
vanishes! Thus when the frequency
of irradiation is equivalent to the Larmor frequency of the spin the external field
vanishes from the rotating frame of reference.

Furthermore, if we vary
slowly the magnetisation,
and end up precessing about
in the transverse plane.

, will precess about

When
= 0 we say that we are at (or on) resonance ,hence the name, nuclear
magnetic resonance. Also, since
now sees no external field in the rotating frame
its internal precession frequency about the z-axis is zero relative to the rotating
frame.

The projections of

and

onto rotating frame :

Now, we have the following equations :

Componets of

along different axes :

Above given are Bloch Equations anchored to rotating frame. Note that the sine and
cosine terms are gone. This is reasonable since
is now 'motionless' in the
rotating frame and therefore should naturally be expected to be time-invariant in this
frame of reference.

Finally time to include relaxation.

There are two types that will be of interest to us. First, if you do an inversion recovery
experiment you can watch the change of
from non-equilibrium back to equilibrium
where it is equal to
. The change from non-equilibrium to equilibrium is, as it
turns out, an exponential one and we can model it as:

where
is the equilibrium magnetisation (and is constant) and
is the
magnetisation at time t (and is therefore variable). We model it this way so that we
have positive quantity that decays towards zero in an entirely analogous way to

radioactive decay. A and A' are constants whose values we need not be concerned
about here since they will disappear. Now, differentiating with respect to time:

This refers to the rate of change of

due to relaxation processes only.

For
and
, in the x-y plane there is a similar decay. Magnetisation here decays
according to :

If we add these equations to our current Bloch Equations we get :

In the old CW (continuous wave) spectrometers, one swept either the frequency
or the field
until the resonance condition was reached. This was done slowly so
as to maintain steady-state conditions. Under these circumstances, ,
and
remained constant in the rotating frame. Therefore, we write:

Solve these equations for

write the above as :

and

using matrix algebra. To simplify we

Also let

Finally it looks like :

In matrix form :

After solving the equations we arrive at the following solutions :